A STUDY  OF  THE  FORMATION  OF 
HYDROXAMIG  ACIDS  FROM 
KETENE 


II Y 


P.vB.°GOCHRAN 


THESIS 


FOR  THE 


D E G R E E O F RACHEL  O R OF  SCIEN  C E 

IN 

CHEMISTRY 


COELEGE  OF  LIBERAL  ARTS  AND  SCIENCES 

UNIVERSITY  OF  ILLINOIS 


1922 


UNIVERSITY  OF  ILLINOIS 


-M§5L_?JL 192JL 


THIS  IS  TO  CERTIFY  THAT  THE  THESIS  PREPARED  UNDER  MY  SUPERVISION  BY 


P.  B.  Cochran 


entitled 


A STUDY  OP  THE  FORMATION  OP  HYDROXAllIC 


ACIDS  PROM  XETENE 


IS  APPROVED  BY  ME  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR  THE 


DEGREE  OF  Bachelor  ox  Science  in  Cherniciry 


-A-'-d 


Instructor  in  Charge 


Approved  :__z 


sd 


HEAD  OF  DEPARTMENT  OF 


500269 


Digitized  by  the  Internet  Archive 
in  2015 


https://archive.org/details/studyofformulatiOOcoch 


ACKNOWLEDGMENT 

The  author  wishes  to  take  this  opportunity 
to  express  his  appreciation  to  Dr.  Charles  D. 
Hurd,  at  whose  suggestion  this  work  ms  carried 
out,  and  to  whose  aid  and  advice  its  successful 
completion  is  largely  due. 


TABLE  OF  CONTENTS 


Page 

ACKNOWLEDGMENT 

I.  INTRODUCTION  1 

II.  THEORETICAL  4 

III.  EXPERIMENTAL 


A. 

Description  and  Operation  of  Apparatus 

7 

E. 

Action  of  kstene 

and  hydroxyl amine 

11 

C. 

Action  of  ketene 
amic  acid 

and  pyromucyl  hydrox- 

11 

D. 

Action  of  ketene 
hydroxaniic  acid 

and  diphenyl  acet- 

13 

E. 

Action  of  ketene 
acid 

and  benzhydroxamic 

13 

CONCLUSION 

14 

V,  BIBLIOGRAPHY  15 


- 1 - 
I 

INTRODUCTION 

(1) 

Standinger  in  1905  prepared  the  first  ketene,  di-phenyl 

ketene,  using  diphenyl  chlor-acetyl  chloride  and  zinc  shavings. 

(3) 

Two  years  later,  Wilsmore  prepared  ketene  from  both 
acetone  and  acetic  anhydride  by  the  use  of  an  electric  coil  im- 
mersed beneath  the  surface  of  the  liquid.  He  suggested  at  this 
time,  that  the  ketene  might  be  used  as  an  acetylating  agent,  since 
it  has  the  advantage,  that  no  by-products  are  formed  in  the  re- 
action. 

(3) 

Schmidlin  and  Bergman  also  obtained  ketene  from  acetone  by 
heating  it  in  a combustion  tube  filled  with  pumice  stone  at  500- 
600°,  with  a resulting  yeild  of  10-14$.  The  reaction  at  this 
temperature  may  be  indicated  as  follows; 

CH3COCH3  iSLQ.-  ch2  = C = 0 -f  CH^ 

and  above  600° 

3 CH3COCH3 * 3 CH  -t  3 CO  4 C3E4 

If  acetic  anhydride  is  used  instead  of  acetone,  it  breaks  down 
first  to  acetone  and  then  to  ketene.  They  also  found  that  the 
gas  would  react  with  water  to  form  acetic  acid. 

(4) 

Ketene  was  prepared  by  Standinger  and  Kubinsky  from  brora- 
aoetyl  bromide  and  zinc  shavings,  with  a yield  of  7-13$,  but 
found  that  no  ketene  was  formed  from  chlor-acetyl  chloride  under 


- 2 - 


the  same  conditions.  The  yield  of  ketene  with  brom-a cetyl 
chloride  was  3-4$. 

(5) 

Staudinger  and  ICLiver,  working  on  the  properties  of  ketene 
stated  that  it  was  poisonous,  melted  at  -151°  and  boiled  at  -51°. 
They  also  proved  that  the  structure  was  CH2:C:o  instead  of  CH=C-OH 

as  some  reactions  might  indicate. 

“ (6) 

Wilsmore  and  Chick  found  that  ketene,  if  allowed  to  stand, 
condensed  to  a brown,  pungent  smelling  liquid,  which  was  acetyl 
ketene,  CH3C0CH=C=0.  This  bears  the  same  relation  to  acetoacetic 
acid  as  ketene  does  to  acetic  acid.  The  condensate  will  react 
with  water  to  give  aceto-acetic  acid,  and  with  aniline  to  give 
aceto-acetanilide. 

In  the  experimental  work  of  this  paper,  ketene  was  prepared 
by  the  pyrogenic  decomposition  of  acetone.  It  is  interesting, 
therefore,  to  record  the  results  of  other  investigators  who  have 
treated  acetone  similarly,  but  with  other  objects  in  view. 

(7) 

Maihle  and  Godon  claimed  to  have  obtained  mesityl  oxide 
by  heating  acetone  at  410-420°  with  thoria  as  a catalyst.  They 
make  no  mention  of  the  presence  of  ketene.  Alumina  and  zirconia 
were  also  used  as  catalysts  with  similar  results.  The  reaction 
may  be  represented  as  follows: 

CH3COCH3  : '-3^  c = CH-COCH3 

ch3^ 

The  above  catalysts  are  known  as  "dehydrating"  catalysts, 
so  that  a Condensation  to  mesityl  oxide  could  be  expected.  It 


- 3 - 


would  also  be  expected  that  phorone,  or  even  mesltylene  would  be 
formed  by  further  dehydration.  This  would  serve  to  explain,  in 
part,  the  higher  boiling  portions  obtained  in  the  fractionation  of 
the  mesityl  oxide.  It  is  quite  possible  that  in  this  work  some 

ketene  was  obtained,  but  if  so,  it  was  disregarded  by  the  authors. 

(8) 

Idle.  E.  Peytral  studied  the  decomposition  of  acetone  vapor 
at  1150°  in  a platinum  tubs,  11  cm.  long.  She  noticed  a pro- 
nounced odor  of  ketene  when  the  acetone  was  forced  through  the 
tube  rapidly.  An  ahalysis  of  the  gases  given  off  at  a slower 
rate  was  made  and  the  following  gases  identified;  ethylene, 
carbon  monoxide,  methane.,  and  traces  of  acetylene  and  hydrogen. 

Her  conclusions  were,  that  there  was  but  one  primary  reaction 
when  acetone  is  decomposed,  namely,  to  form  ketene  and  methane. 
Ketene,  in  turn,  then  is  broken  further  into  ethylene  and  carbon 
monoxide. 


: ' 


. 


. 

, 


4 


II 

THEORETICAL. 

The  object  of  the  present  investigation  was  to  study  the 

effect  of  ketene  upon  hydroxylamine,  and  upon  certain  hydroxy 

amio  acids.  The  only  work  done  upon  this  subject  was  that  of 
(9) 

Jones  and  Hurd.  They  prepared  diphenyl  acethydroxamic  acid 
by  the  action  of  diphenyl  ketene  and  free  hydroxylamine,  accord- 
ing to  the  equation 

(C6Hs)2C=C=0  f HHsOH— *(C6Hs)2  -0-0-0 
# I I 

H 1'IHOH 


The  similarity  of  ketene  and  phenyl  isocyanate  might  also 

(10) 

be  noted.  Kjellin  prepared  phenyl  hydroxy  urea  by  the  action 

of  phenyl  isocyanate  and  hydroxylamine. 

C6H5  - N=  C=  0f  HH20H — * C gHs  IT  - C = 0 

I I 

H NHOH 


Ketene  with  a structure  very  similar  to  the  above,  might 
be  expected  to  react  with  hydroxylamine  in  the  same  manner. 

C eH2  = C = 0 +■  NH20H >H2C  - C = 0 

I I 

H HHOH 

would  expect  in  view  of  these  results,  that  this  reaction 
would  take  place.  The  results  of  the  experiment  verified  this 
prediction. 


- 5 - 

The  reaction  of  ketene  on  certain  hydroxamic  acids  was  also 
studied.  Here  there  is  a possibility  of  three  reactions  as 

follows : 

1.  R -CO  - N— OH  * CHS  - C = 0 — *R-CO  - N - OCOCH3 

^CO0h3 

3.  R - CO  - N-OH  * CHS  = C = 0 — »R  - CO  — N - OH 

H CH2 — C = 0 

3.  R - CO-±  - OH  +■  CH2  - C = 0 — *R  - "CO  HHOH 

Experimental  evidence  shows  that  only  reaction  (1)  takes 
place.  For  example,  pyromucyl  hydroxamic  acid, 
reacts  with  one  mole  of  ketene  to  form  the  known  acetyl  ester, 

Further  treatment  of  it  replaces  the 
second  hydrogen  to  give  the  diacetyl  ester, 
which  is  a new  compound. 

When  diphenyl  acethydroxamic  acid  was  treated  with  ketene, 
the  diacetyl  ester  resulted. 

. 0C0CH3 

(C^5)sCH.C0.UH0H  + CH2  = C=0— .(CeHsJsCH.CO-K  - 000HS 

(9) 

Jones  and  Hurd  describe  this  compound  and  also  the 
preparation  of  the  monoacetyl  derivative  of  this  acid  by  means 
of  acetic  anhydride.  The  mono-acetyl  ester  was  obtained  only 
by  destroying  the  excess  of  acetic  anhydride  as  soon  as  the 
presence  of  the  diphenyl  acet -hydroxamic  acid  was  no  longer  in- 
dicated by  the  ferric  chloride.  It  appears  that  the  di-acetyl 
derivative  is  much  more  readily  formed.  Thus,  it  is  natural  to 
suppose  that  it  would  be  formed  when  ketene  is  used,  even  in  a 


6 


slight  excess. 

Eenzhydroxamic  acid  was  also  treated  with  an  excess  of 
ketene.  In  this  case  an  oil  was  formed,  which  was  probably  the 
diacetyl  ester. 

.OCOCH3 

(C6Hs).0O^HHOH  + CH2  = C = 0— ♦(C6H5).C0.N  - COCH3 


7 


III 

EXPERIMENTAL 

A.  Description  and  Operation  of  Apparatus. 

(3) 

The  method  of  Schmidlin  and  Bergman,  modified  to  some 
extent,  was  used  throughout  the  experimental  work.  The  ketsne 
was  obtained  by  the  decomposition  of  acetone  in  a combustion 
furnace  at  600°. 

CH3COCH3 • = C = 0 * CH4 

Ketene  is  quite  soluble  in  acetone.  It  was  found  that  about 

50^  of  the  acetone  went  through  the  combustion  tube  unchanged. 

In  previous  methods,  this  acetone  was  condensed  in  a series  of 

U-tubes,  which  were  immersed  in  an  ice-salt  mixture.  Thus,  when 

ketene  passed  through  the  U-tubes,  much  of  it  was  dissolved  and 

lost.  To  avoid  this,  the  vertical  condenser,  shown  in  the  diagram 

was  employed.  It  was  provided  with  an  outlet  at  the  bottom  to 

remove  the  acetone  as  it  condensed.  The  acetone,  after  absorbing 

some  ketene,  became  brown  in  color.  It  possessed  a pungent  odor, 

suggesting  the  possibility  of  the  formation  of  the  acetyl  ketene 

(6) 

studied  by  Wilsmore  and  Chick,  After  considerable  experimenting, 
to  obtain  an  efficient  apparatus,  that  indicated  by  the  following 


diagram  was  designed: 


9 


(A)  is  a pressure  equalizer,  provided  to  neutralize  the 
back  pressure  from  the  combustion  tube.  This  will  permit  a steady 
dropping  of  acetone  from  the  separatory  funnel  and  insure  an  even 
flow  of  ketene  through  the  apparatus.  The  flask  (B)  is  heated 
in  a water  bath,  causing  the  immediate  vaporization  of  each  drop 
of  acetone  as  it  strikes  the  bottom  of  the  flask.  The  combustion 
tube  is  filled  with  cracked  porcelain  as  a contact  agent.  (C) 
is  an  outlet  tube  provided  with  a pinch  clamp,  from  which  the 

condensed  acetone  may  be  drawn  at  short  intervals,  thus  preventing 

a 

the  absorption  of  ketene.  The  two  U-tubes  are  immersed  in^freez- 
ing  mixture,  as  safety  traps  to  catch  any  acetone,  which  might 
escape  condensation  in  the  vertical  condenser.  This  precaution 

is  necessary  since  the  acetone  would  react  with  the  hydroxyl  afrnine 
to-  form  acetone  oxime. 

Operation  of  Apparatus. 

The  combustion  tube  is  heated  to  600°  and  kept  at  this 
temperature  for  a short  time,  in  order  to  drive  out  any  moisture 
which  would  react  with  the  ketene  to  form  acetic  acid.  The 
acetone  is  placed  in  the  separatory  funnel  and  allowed  to  drop 
slowly  into  the  flask  (B) , which  is  immersed  in  a heated  water 
bath.  Here  it  is  immediately  vaporized  and  passes  over  into  the 
combustion  tube,  where  it  is  decomposed  at  600°. 


CH3COCH3 


600° 


CH2  = C = 0 + CH* 


- 10 


Some  acetone  (about  50$>)  goes  through  unchanged.  The 
acetone  vapor  and  the  gases  resulting  from  the  decomposition 
pass  on  to  the  vertical  condenser.  The  former  is  condensed  and 
is  drawn  off  into  the  flask  E.  It  may  be  returned  to  the  dropping 
funnel  and  subjected  to  decomposition, again.  The  more  volatile 
material  passes  on  to  the  U-tubes.  Traces  of  acetone,  which  it 
is  essential  to  remove  when  ketene  reacts  with  hydroxylamine , are 
liquified  at  this  point.  The  gases  then  pass  to  the  reaction 
flask  (F).  Here  the  ketene  will  be  absorbed  and  the  methane  and 
other  such  gases  will  pass  off. 

In  order  to  determine  the  yield  of  ketene  from  such  an 
apparatus,  aniline,  dissolved  in  ether,  was  used  as  the  reacting 
substance,  since  the  ketene  will  react  quantitatively  with  this 
compound  to  form  acetanilide, 

c6h5nh2  * ch2  = c = o — .c6h5hhcoch3. 

55  grams  of  acetone  were  Ideated  as  described  and  the  gases  were 
passed  through  15  grams  of  aniline,  dissolved  in  ether.  38  grams 
of  acetone  were  condensed  by  the  vertical  condenser.  Thus,  only 
37  grams  of  the  acetone  reacted  to  form  ketene.  The  ether  and 
excess  aniline  were  distilled,  leaving  a residue  of  acetanilide. 
The  acetanilide,  after  purification  with  ether  and  drying,  melted 
at  113°.  '"eight  11  grams.  This  is  a yield  of  17.5 fo  ketene,  based 
upon  the  acetanilide  formed,  and  upon  the  acetone  which  was  not 
recovered.  The  yield  reported  by  Schmidlin  and  Bergman  was  11 % 


- 11 


B.  Ketene  and  Hydroxyl amine . 

CH2  = C = 0 + ITHgOH >CH3C0.m.0H 

The  hydroxylamine  was  prepared  by  treating1  a solution  of 
hydroxyl amine  hydrochloride  in  methanol,  with  sodium  methylate. 
This  was  filtered  from  sodium  chloride  and  partially  evaporated 
in  a vacuum.  It  was  then  filtered  again  and  the  filtrate  was 
distilled  in  vacuo.  Three  cubic  centimeters  of  free  hydroxylamine 
were  obtained,  which  distilled  at  55-60°,  at  30  mm.  pressure.  It 
was  mixed  with  dry  ether  and  treated  with  an  excess  of  ketene. 

The  ether  was  distilled  and  the  oily  residue  remaining  was  placed 
in  a vacuum  desiccator  over  sulfuric  acid.  After  a week,  trans- 
parent crystals  formed.  These,  when  pressed  on  a clay  plate, 

melted  at  86-88°,  the  melting  point  of  acethydroxamic  acid.  The 

ic 

crystals  showed  a discoloration  with  fern/chloride  solution, 
indicating  that  the  product  was  not  the  acetyl  ester,  which  melts 

at  89°. 


C.  Ketene  and  Pyromucyl  Hydroxamic  acid. 


1. 


Nr 


CO.NHoH 


4*  CHL-C  = 0 


Sr 


H 

co.ti-cocrii 


3. 


-h  2 c H=C=  o 


.OCO  CH3 

cow-~coch3 


V CO.NHOH  ^ 

1,  One  gram  of  pyromucyl  hydroxamic  acid  was  dissolved  in 
ethyl  acetate  and  treated  with  ketene  until  no  discoloration 


. 


- 13 


resulted  when  a drop  of  the  solution  was  treated  with  ferric 
chloride  solution.  7 cc.  of  acetone  was  used.  The  apparatus, 
however,  was  filled  with  ketene,  before  the  acid  solution  was 
introduced  in  the  reaction  flask.  This,  of  course,  left  the 
same  amount  of  ketene  in  the  apparatus  at  the  conclusion  of  the 
experiment,  as  was  there  at  the  start.  The  solvent  was  then 
distilled  and  the  residue  was  dried  over  sulfuric  acid  in  a 
vacuum.  The  compound  was  purified  with  ether  and  pressed  on  a 
clay  plate.  It  melted  at  34-96°,  indicating  that  the  compound 
was  the  monoacetyl  ester  of  the  pyromucyl  hydroxamic  acid. 

2.  A new  sample  of  the  acid  was  dissolved  in  ethyl  acetate 

to  -form  the  d i acetj / esfer. 

and  treated  with  an  excess  of  keteneA  An  oil  resulted  after 
distillation  of  the  solvents.  This  was  dried  over  sulfuric  acid 
in  vacuo  for  four  days.  Crystallization  took  place  readily  when 
the  oil  was  cooled  to  0°.  The  crystals  were  dissolved  in  alcohol 
and  twice  the  volume  of  water  added.  This  caused  a white  crystal- 
line precipitate  when  the  walls  of  the  container  were  scratched 
with  a glass  rod.  It  was  filtered  and  dried  in  a vacuum.  M.P. 
54-55°.  The  compound  is  soluble  in  hot  alcohol  and  benzene.  It 
is  insoluble  in  water  and  in  petroleum  ether. 

Analysis.  Subs.,  0.3573:  N,  15.60  c.c.  (35.5°  and  737.0  mm. 

(at  35.0°)  ).  Calc,  for  C9H9O5IT:  II,  6.65.  Found  6.63 

D.  Ketene  and  Diphenylacethydroxamic  acid. 

COCH3 

3 CHg  = C = 0 f {C6H5)SCH.  CO.HHOH *(C6H5)3CH.C0-< 


- 13 


A solution  oi  tn s acid  in  ethyl  acetate  ms  treated  with  ketene 

in  the  same  manner.  The  solvent  ms  distilled  and  the  residue 

was  dried  over  sulfuric  acid  in  a vacuum.  The  resulting  di-acetyl 

ester  was  pressed  on  a clay  plate.  The  melting  point  was  S5.5-97®, 

showing  the  compound  to  be  the  di-acetyl  ester  indicated  by  the 

(9) 

above  equation.  This  is  to  be  expected,  3ince  Jones  and  Hurd 
obtained  this  e3ter  with  acetic  anhydride  and  found  that  the  mono- 
acetyl derivative  could  only  be  obtained  by  stopping  the  reaction 
as  soon  as  the  diphenyl  acethydroxamic  acid  was  used  up. 

E.  Ketene  and  Benzhydroxamio  acid. 

The  acid  was  dissolved  in  ethyl  acetate  and  treated  with  an 
excess  of  ketene.  After  the  reaction,  the  ethyl  acetate  was 
distilled  leaving  an  oil.  This  showed  no  reaction  with  ferric 

ben  z-hydroxcrnic 

chloride,  indicating  that  there  was  no  free^acid  present.  The 
composition  of  this  derivative  was  not  determined. 


- 14  - 


IV 

CONCLUSION 

1.  Ketene  and  hydroxyl amine  react  normally  to  form 
acethydroxamic  acid. 

3.  The  reactions  between  ketene  and  certain  hydrox- 
amic  acids  have  been  studied.  Either  the  mono  - 
or  the  di-acetyl  ester  can  be  formed,  depending 
upon  the  quantity  of  ketene  present. 

3.  The  addition  of  ketene  to  hydroxarnic  acids 
follows  the  reaction: 

R - CO.NHOH  4-  CH2  = C 
and  with  an  excess 

R. CO. NH.O. COCKs  t CH3 


= 0 — *R-  CO  - NH  - 0C0CH3 


= C - 0 — *R.  CO.  N 


,COCHa, 


OCOCH; 


- 15  - 


V 

BIBLIOGRAPHY 


1. 

Ber. 

36, 

1735 

(1905) 

3. 

Jour.  Chem.  Soc. 

31, 

1938 

(1907) 

3. 

Ber . 

43, 

3831 

(1910) 

4. 

Ber. 

43, 

4313 

(1909) 

5. 

Ber. 

41. 

594 

(1908) 

6. 

Jour.  Chem.  Soc. 

93, 

346 

(1906) 

7. 

Bull.  Soc.  Chim. 

31, 

61 

(1917) 

6. 

Bull.  Soc.  Chim. 

31, 

133 

(1913) 

9. 

J. Am.  Chem.  Soc. 

43, 

3 433 

(1931) 

